Method for producing alpha-olefin polymers utilizing titanium trichloride and an antimony-aluminum complex as the catalyst



1956 YUKICHI TAKASHI ETAL 3,

- METHOD FOR PRODUCING (-OLEFIN POLYMERS UTILIZING TITANIUM TRICHLORIDEAND AN ANTIMONY-ALUMINUM COMPLEX AS THE CATALYST Filed Sept. 20, 1962Fig.

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Volts United States Patent METHOD FOR PRODUCING a-OLEFIN POLYMERS Thisinvention relates to a method for producing aolefin polymers having highcrystallinity by use of a novel catalyst.

An object of the present invention is to provide a novel catalystcapable of producing a-olefin polymers having high stereo-regularity.

Another object is to provide a method of polymerization for producinga-olefin polymers having high stereoregularity by using said novelcatalyst.

A further object of the present invention is to provide a-olefinpolymers having structures of high stereoregularity, capable ofproducing fibers, films and molded articles of excellent properties, inspite of using the polymerization products as they are withoutpurification such as extraction or fractional dissolution.

A known process for producing crystalline polymers from a-olefins, isdisclosed in Natta et al., Japanese patent publication No. 10,596/57.Therein, linear polymers of a-olefins having specific stereo-structuresare obtained by use of catalysts comprising (I) a compound of a metalbelonging to Groups IVA to VI-A of the Periodic Table including thoriumand uranium, and (II) a metal belonging to Groups II and III of thePeriodic Table, an alloy thereof, a hydride or an organometallic compound of a metal belonging to Groups I to III of the Periodic Table.Subsequently, the patentees discovered that, in case of polymerizingoz-OlCfiIlS by use of the aforesaid catalysts, the use of a solid andinsoluble catalyst comprising triethyl aluminum and titaniumtrichloride, for example, results in the formation of stereo-specificpolymers having a markedly high crystallinity, isotactic structure, andhigh molecular weights (Japanese patent publication No. 2,489/59).

The latter invention was significant and was far beyond the inventiondisclosed in the aforesaid Japanese patent publication No. 10,596/57.However, even when the polymerization of a-olefins, propylene forexample, is carried out according to said process, the ratio ofisotactic polymers having stereo-regularity, represented by the ratio ofnheptane extraction residue, is less than 80% (refer to Japanese patentpublication No. 2,489/ 59). Therefore the resulting product contains aconsiderably large amount of non-crystalline polymers (atactic andstereo-block polymers), which are considered to have irregularstructures. Fibers produced from polymers containing isotactic polymersof such a low extent give a waxy touch, as disclosed in Japanese patentpublication No. 4,722/60 by the inventors themselves. This has been agreat obstacle in practical use. In order to overcome said drawback,Natta et al. have reported in Japanese patent publication No. 4,895/ 60that when the polymers obtained are subjected to extraction with anorganic solvent, 2-ethyl hexane for example, to re- 3,293,223 PatentedDec. 20, 1966 move non-crystalline atactic polymers, it is possible toproduce excellent fibers, films and the likes.

The present inventors have provided a method for manufacturingcrystalline polymer having a higher stereo regularity which produces asuperior fiber or film when it is used as is without such treatments asextraction or fractional dissolution.

That is to say, the present invention relates to a method for producingpoly-a-olefins having high stereospecificity by polymerizing a-olefin inthe presence of a catalyst obtained by reacting [A] TiCl with [B] one ormore members selected from the organo-metallic complexes having thefollowing general formulae:

(I) SbR XAl R' wherein X is one member selected from the groupconsisting of Cl and Br; R is an ethyl group; and R is the same ordifferent alkyl groups having 2 to 6 carbon atoms, but such alkyl groupshaving 4 or more carbon atoms should be limited to 3 or less in number.

(II) SbR R"XAl R' X', wherein X and X are the same or different halogensselected from the group consisting of Cl and Br; R is an ethyl group; Ris the same or different alkyl groups having 2 to 6 carbon atoms: butsuch alkyl groups having 5 or more carbon atoms should be limited to 2or less in number; and R" is an alkyl group having 2 to 6 carbon atoms.

(III) SbR XAlR X wherein X and X are the same or different halogen atomsselected from the group consisting of Cl, Br, and I; R and R are thesame or different alkyl groups having 1 to 6 carbon atoms; and n is l, 2or 3.

It is a marked characteristic of the present invention that whenu-olefins are polymerized in accordance with the present invention,highly crystalline polymers having isotactic structure are obtainable.For example, in the case of polymerizing propylene, a conventionalcatalyst comprising Al(C H and TiCl gives polymers having isotacticity(represented by the ratio of an extraction residue to the initialsubstance after the extraction of 24 hours with boiling n-heptane byusing Soxhlet extractor; hereinafter referred to as n-heptane extractionresidue) of as low as about -80%, whereas the present novel catalystgives polypropylene having isotacticity of more than Another markedcharacteristic of the present invention is that when the polymerizationof a-olefins, propylene for example, is carried out according to themethod of the present invention, the resulting products, such as fibers,films or molded articles, obtained by.using the polymerization productswithout any particular treatment such as extraction or fractionaldissolution, are

nearly free from waxy touch and are sufficiently satisfactory.

Further, it is one of the characteristics of the present invention thatthe catalysts employed in the present invention have such highpolymerization activity that a-olefins can be polymerized at a highpolymerization rate. Namely, the present catalysts show such a highactivity that in case of the polymerization of a-olefins, for examplepropylene, under a partial pressure of 3 kg./cm. it is possible toobtain polypropylene in an amount of to 300 g. per hour per gram oftitanium trichloride.

The organometallic complexes containing antimony and aluminum employedin the present invention are represented, as mentioned above, by thegeneral formulae (I) SbR XAl R' (II) SbR R"XAl R' X and (III) '5 a SbRXAlR'nX For example, the efiective complexes are:

b 2 5 4 2 z s 5 Processes for synthesizing these organo-metalliccomplexes used in this invention are: a

(1) A process for preparing the Complex I by reacting tetra-alkylstibonium halide with trialkyl aluminum.

(2) A process for obtaining the Complex II by reacting tetra-alkylstibonium halide with dialkyl aluminum halide and trialkyl aluminum.

(3) A process for producing the Complex II by reacting antimonytrichloride with trialkyl aluminum.

(4) A process for preparing the Complex III by reacting tetraalkylstibonium halide with alkyl aluminum dihalide, dialkyl aluminum halideor trialkyl aluminum.

As a typical example of the organo-metallic complexes containingantimony and aluminum, the details of a method for synthesizing Sb(C HClAl (C H Cl and the properties of said complex will be illustrated inthe following. For synthesizing this complex, the Process 3 is the mostsimple and convenient. l

Into a 1 l. round-bottomed four-necked flask provided with a mercurysealed stirrer, a dropping funnel, a thermometer and a cooler, 1 mole ofantimony trichloride and 300 cc. of dehydrated n-hexane are changed indried nitrogen atmosphere free from oxygen. 4.5 lIl'lOlCS of triethylaluminum are dropped slowly through the dropping funnel into the flaskwhile refluxing n-hexane. During this time vigorous agitation iscontinued. The reaction should be carried out under nitrogen atmosphere.The reaction product comprises a powdery black solid and two colorlesstransparent liquid layers. The solid product is filtered off and theliquid layers are separated to obtain the lower layer. The thusrecovered lower layer isextracted with 600 cc. of n-hexane 16 times toremove completely the unreacted organo-aluminum compound. On strippingthe n-hexane, 240 g. of n-hexane-insolubie colorless liquid substance isisolated. The reaction prodfuric acid, Sb was analyzed quantitatively byusing KMnO -titrat ion method and Al was analyzed by using oxine method.The other part of the sample was decomposed With water and the chlorinecontent was analyzed by using Vorh-a-rds method. Finally, carbon andhydrogen were quantitatively analyzed by using an ordinarymicro-combustion method.

(2) The content of the active ethyl groups was calculated from theethane lgas evolved at hydrolysis. The theoretical values werecalculated on the assumption that one molecule contains 5 active ethylgroups. It was also confirmed by gas-chromatographic analysis that theevolved gas contained was, in most part, ethane though it contained aslight amount of hydrogen and ethylene.

TABLE 2 Di 1.112 Measured by a pycnometer.

11 1.4995 Measured by Abbes retractometer.

M.W 542; theoretical Measured according to cryoscopic value: 508.17.method by using benzene solution.

not thus obtained fumes or fires in air and explodes on 5 contact withwater and air. The infrared absorption spectrum of this substance isshown in FIG. 1, and the analytical results and physical properties areshown in Tables I and 2, respectively.

TABLE 1.ANALYTIC-AL RESULTS Further, the presence of Sb(C H ion wasconfirmed after the hydrolysis by measuring the polarogram of thehydrodyzates (refer to the accompanying FIG- URE 2.)

The number of active ethyl groups and the presence of Sb (C H show thefact that the complex thus synthesized has the structure Sb (C H ClAl(CH C1. The characteristics of the thus obtained organo-metall-ic complex,Sb(C H ClA.l (C H C1, are that it is a colorless transp-arent liquid andis substantially insoluble in lower aliphatic hydrocarbon, such asn-hexane, which is recommended as a polymerization medium.

As mentioned before, even though the washing of the produced SbAl (C HCl was repeated many times with n-hexane, the weight of residue does notdecrease. In order to confirm this property quantitatively, Sb(C H ClAl(C H C1 labelled with 5b was synthesized and its solubility in varioushydrocarbons was examined but the solubility of this complex in n-hexanewas non-detectable.

Table 3. olubility of Sb(C H5)4ClAlz(CzH5)5Cl in various hydrocarbonsHydrocarbons: Solubility, Percent n-Hexane Non-detectable. n-Heptane0.05. n-Octane =01.

Norm-In nheptane and n-octane soluble parts, Al was detected in anamount corresponding to 2 mole against 1 mole of Sb.

Note (1): Following analytical method was adopted: After thedecomposition of a part of the sample with an aqueous solution ofpotassium permanganate and sulknown liquid aluminum and antimonycompounds, re-

spective nuclear magnetic resonance adsorptions were 5 examined. Theresults are shown in Table 4.

TABLE 4.NUCLEAR MAGNETIC RESONANCE ADSORPTION DATA OF s ggr ioiml(oltmsoi AND VARIOUS ALUMINUIVI AND ANTIMONY COM- No'rE.The Hugginseleetronegativity was calculated by using the difierence between H: andCH; shifts (A in c.p.s.) at 60 me. according to the revised Dailey andShoolery equation [.I. R. Cavanaugh and 13.}; Dailey, J. Chem. Phys, 34,1101, (1061)]. Namely,

the electronegativity e 0.0114A+l.

As shown in Table 4, the electronegativity of Al atoms, which constitutethe complex Sb(C H ClA'l (C I-I C1, is lower than that of (C H AlCl or(C I-l Al. Therefore, it is recognized that the environment of the ethylgroups linked to A1 of the complex is different from that of others.

The synthesis Process 3, mentioned before in detail as a process forsynthesizing the complex is the most simple and convenient method forsynthesizing the Complex II, all alkyl groups of which are the same. Itis also possible, however, to synthesize the various complexes by usingtetraa'lkyl s'ti-bon-ium salt as a starting material [Processes (1), (2)and (4)]. In order to show concrete techniques of the precesses, theprocess for synthesizing Sb(C H ClAl(C I-I )Cl is mentioned, as anexample in the following (Process (4) )1 Into a 100 cc. four-neckedflask, 13.7 g. (0.05 mole) of Sb (C H Cl crystals are charged undernitrogen atmos-phere together with 100 cc. of n-hexane. 6.35 g (0.05mole) of Al(C H )Cl dissolved in 40 cc. of n-hexane is dropped in theflask to react therewith, While maintaining the inner temperature at 50C. After the dropping is completed, the temperature is graduallyelevated to 50 C. and the agitation is continued for about minutes tocomplete the reaction. Subsequently, the content is repeatedly washedwith dried n-hexane. By cooling the content after stripping offn-hexane, 20 g. of colorless crystals (M.P. 34-39 C.) are isolated. Theanalytical values shown in the following coincided with the chemicalformula Sb-(C H ).,ClAl(C H )Cl TABLE 5 l Sb Al Cl I C II Found,percent"- 29. 69 6. 59 26. 90 28. 49 5. 9G Calcd, percent 30. 41 6. 7457 29.97 6. 29

terial such as tetraalkyl stibonium salt, antimony trichloride andorgano-aluminum compound. The typical example of aforesaid differencesis as follows. That is, as described in detail in Example 21, it is anunexpected fact that the catalyst prepared by reacting Sb (C H ClAl (C HC1 with TiCl is able to polymerize propylene even at low temperature tonearly perfect iso'tactic high polymer.

On the other hand, it is a fact that the starting material forsynthesizing Sb (C H ClAl (C H )Cl such as Sb(C H Cl and Al(C H )C'lcould not give the effective catalyst for the polymerization ofpropylene even intcombination with TiCl (Refer to referential Example lof Japanese patent publication No. 20,743/61 by Eastman Kodak Co.)

This shows that the nature of the chemical bond in Sb(C H ClAl(C H )Clis entirely different from that in Sb(C H Cl or Al(C I-I )Cl There havebeen proposed many processes for preparing the titanium trichloride suchas, for example, by reducing titanium tetrachloride with hydrogen orwith metallic aluminum in the presence of a small amount of aluminumchloride. The titanium trichloride thus obtained can be employed in thepresent invention.

In embodying the present invention, the desirable amount of titaniumtrichloride employed is O.00010.05 mole per mole of u-olefin to bepolymerized, and it is recommended to use 0.1-1-0 moles of saidcomplexes containing antimony and aluminum per mole of said titaniumtrichloride. The amount of complex required depends upon the amount oftitanium trichloride employed. In case of using a large amount oftitanium trichloride, a sufiicient catalyst activity may be obtained byusing a small amount of complex per mole of the titanium trichloride,whereas in case of employing a small amount of titanium trichloride, thecomplex should be used at a higher ratio.

In order to make such behavior clearer, the method is illustrated asfollows with reference to the following examples.

Table 6 shows an example of the polymerization of 1 mole of propylene inn-hexane, using a large amount of titanium trichloride, according toexactly the same process as in Example 1.-

TABLE 6 Experiment TiCl SbEt-gClAizEliCl/Ti0i3, Temp, Time, Polymer [71]n-Heptane N0. moi molar ratio 0. hr. yield, (g./1DO cc.) residue,percent percent As evident from the above table, although thepolymerization is carried out with a comparatively large amount of TiCl(0.005 mole per 1 mole of monomer), polymerization could not be observedby using less than 0.10 mole of complex and polymerization could proceedonly by using more than 0.1 mole of complex. Further, in case thepolymerization is carried out by use of a small amount of TiCl theamount of complex required per mole of TiCl increases. It ismeaningless, however, to use the complex in an amount larger thanrequired.

Table 7 shows the results of experiments effected on the polymerizationof propylene in xylene, in accordance with the process described indetail in Example 2, using 2 m. moles of titanium tric-hloride per litreof xylene and inert to each of the catalyst components, such as, forexample, n-hexane, n-heptane, benzene, xylene or cyclohexane. The ratioof the solvent used to u-olefin may optionally be decided depending onthe modes of polymerization. Ordinarily, however, it is appropriate touse less than parts by weight of the solvent per part by weight ofu-olefin.

Also, in the practice of the present invention, the polymerizationtemperature for obtaining an excellent polymer having high molecularweight is 15 to 120 C., preferably 40 to 80 C. Further, thepolymerization pressure may also be selected freely. The object of theinvention may, however, be sufficiently achieved at 1 to atmosphericpressures, ordinarily at 1 to 10 atmosvarying the amount of complexadded. 25 pheric pressures.

TABLE 7 i CaHo n-Heptane Experiment T101, SbEt ClAl2Et5Ql/TiCl partialTemp, Time, Polymer, [1 1 residue, N 0. m. moi/l. molar ratio pressure,0. hr. gr. (g./100 cc.) percent;

kg./0m. I 2 1.0 i 5.0 60 2.0 34.0 10.31 92.9 2 1.5 I 5.0 00 2.0 48.011.08 94.5 2 2.0 5.0 60 2.0 51.2 13.00 95.0 2 3.0 5.0 00 2.0 72.3 10. 0795.0 2 5.0 5.0 00 2.0 73.9 10. 57 94.6 g 00 2.0 99.0 s. 45 60 2.0 101.08.39

As is clear from the above table, the polymer yield in- In order toclarify the effects and characteristics of creases according as theincrease of the molar ratio of the complex/TiCl However, even when morethan l0 moles of the complex are added per mole of TiCl there areobserved neither a marked increase in yield no variations inisotacticity of the polymer. Therefore, it is meaningless to use thecomplex in an amount of more than 10 moles per mole of TiCl The presentinvention is applicable to the polymerization of a-olefins, such aspropylene, butene-l, pentene-l, 3-methyl-butene-l, 4-methyl-pentene-1and styrene, and

the polymerization carried out in accordance with the present invention,comparative experiments were carried out, using the same finelypowdered, TiCl The polymerization effect of employing said complex wascompared with the case using Al(C H as described in the specification ofsaid Japanese patent publication No. 2,489/60. The results are shown inthe following table.

TABLE 8 Referential Example 3 Example 4 example Catalyst composition:

1013 (m. mole) 1.0 1 0 1. 0 2H5)a (m. mole) 5. 0 2 5)4C Al2(C2I-I5)6 (m.mole) 2. 5 2 5)4BTAl2(C2H )s (In. mole) 25 Reaction medium: Xylene(1111,) 500 500 500 Polymerization condition:

Partial pressure of propylene (kg./cm. 5. 0 5. 0 5. 0 emp rature 0.) 5555 une hr. 2. 0 2. 0 2. 0 Rate of polymerization (g. polymer/g. TiCla5)-, 230 300 250 Intrinsic viscosity (g./l00 cc.) 3.05 9. 76 9. 23 pta eresidue (percent) 65. 5 91. 4 90. 3

in either case, it is possible to obtain a polymer having highcrystallinity.

In the cases of propylene and butene-l, it is desirable to use themonomers as pure as possible, but relatively low purity monomers, e.g.,about 80% purity, containing inert gases are also available.

In practicing the present invention, a reaction medium may or may not beemployed, and the preferable reaction medium is an aliphatic, alicyclicor aromatic hydrocarbon It is clear from the above table that acomparison, carried out under the same conditions, between thepolymerization of propylene according to the conventional process andthe same polymerization conducted by use of the catalysts of the presentinvention shows that the ratio of isotactic polymer, represented by then-heptane extraction residue, obtained in accordance with the presentinven tion is improved by as much as 30% In the following, the presentinvention will be more Example 1 Sb Al O H Cl Calcd (percent) 23. 96 10.62 42. 54 8. 93 13. 96 Found (percent)- 23. 91 10. 43 42. 77 9. 13. 96

Physical properties: D4 1.112; o 1.4994.

After agitating the resulting mixture for 30 minutes at roomtemperature, the autoclave was cooled to 80 C. The autoclave was thenevacuated and 0.5 mole of high purity propylene was introduced therein.Subsequently, the autoclave was heated to 60 C. and shaken to carry outthe polymerization. The polymerization pressure showed 6.3 kg./cm. atfirst, but completely lowered in 3 hours. Basing upon the variation ofthe polymerization pressure, quantity of the produced polymer .per gramof TiCl in case of partial pressure of propylene had been kept at 3kg./cm. was calculated as high as 230 g. per gram of TiCl The residualcatalyst in the thus obtained polymerization product was decomposed with500 cc. of methanol, boiled in 30% hydrochloric acid-methanol, washedwith water and dried to obtain 18.8 g. of white powdery polymer. Then-heptane extraction residue of the resulting polymer was 94.5% and theinstrinsic viscosity thereof in tetraline solution was 7.99.

Example 2 Into a one litre stainless steel autoclave provided with amagnetic stirrer, 500 cc. of xylene was introduced. Then, 1.0 m. mole offinely powdered TiCl and the complex used in Example 1, i.e., Sb(C HClAl (C H Cl, were charged into the autoclave under a dried nitrogencurrent free from oxygen, varying the amount of the complex (from 1.0 to13 m. moles). Immediately after closing, the autoclave was evacuated andheated to 60 C. Subsequently, high purity propylene was introducedtherein under pressure so as to maintain its partial pressure at 5kg./cm. to carry out the polymerization. After two hours polymerization,the polymerization product was treated by the same methods as describedin Example 1, respectively. In each case, a white powdery polymershowing a high isotacticity was obtained at a high polymerization rate.Yields, n-heptane extraction residues and intrinsic viscosities ofrespective polymers have been shown in Table 7.

Example 3 In a 20 cc. glass ampoule, 1.0 m. mole of finely powdered TiCland 2.5 m. mole of the complex 5b 2 5) 4 2 (CZHS) 6 synthesizedaccording to the process disclosed in the main body of the presentspecification, were sealed together with 7 cc. of xylene under a driedoxygen-free nitrogen atmosphere. The analytical values and physicalproperties of this complex were as follows Analytical values:

I Sb Al C H Br Oalcd (percent)- 2 29 9.87 43. 97 9. 23 14. 63 Found(percent) 2. 46 9. 86 43. 56 9. 07 15. 21

Physical properties: D4 1.181; my, 1.5125.

This 'ampoule was pla ced in a stainless autoclave equipped with amagnetic stirrer and then 500 cc. of purified and dried xylene wasadded. After evacuating the autoclave, high purity propylene wasintroduced therein under pressure so as to maintain its partial pressureat 5 kg./cm. Subsequently, the autoclave was heated to 55 C. and thecatalyst ampoule was broken whereby the catalyst was contacted with themonomer to initiate the polymerization reaction. After 2 hourspolymerization, the resulting polymerization product was treated by thesame methods as described in Example 1 to obtain 90 g. of a whitepowdery polymer. The rate of polymerization calculated was 300 g. perhour per gram of TiCl The boiling n-heptane extraction residue was 91.4%and the intrinsic viscosity was 9.76.

Example 4 Sb Al O H Br Calcd (percent)- 22. 29 9. 87 43. 97 9. 23 14. 63Found (percent)- 22. 46 9.86 43. 56 9. 07 15. 21

Physical properties: D4 1.181; m), 1.5125.

In this case also, as in Example 3, 75 g. of white powdery polymer wasobtained and the polymerization rate showed as high as 250 g./ g. TiClhr. Its n-heptane extraction residue was 90.3% and its intrinsicviscosity was 9.23.

Example 5 Into two pieces of 10 cc. glass ampoules, 0.6 m. mole offinely powdered TiCl and 1.0 m. mole of the complex employed in Example3, i.e., Sb(C H ClAl (C H were sealed, respectively. These ampoules wereput in a 300 cc. stainless steel shaking type autoclave, which wasclosed after the addition of 150 cc. of benzene. After the autoclave wascooled to C. and evacuated 0.5 mole of high purity propylene wasintroduced. The autoclave was then heated to 80 C. and the ampoules werebroken whereby the two catalyst components were contacted with eachother in the presence of the monomer to start the polymerization. Thepolymerization was continued for 2 hrs. while shaking the autoclave. Theresulting polymerization product was treated by the method as describedin Example 1 to obtain 19.8 g. of white powdery polymer. The n-heptaneextraction residue of the resulting polymer was 88.9% and the intrinsicviscosity was 7.32.

Example 6 Into two pieces of 10 cc. glass ampoules, 0.6 m. mole offinely powdered TiC'l and 1.0 m. mole of the complex employed in Example4, i.e., Sb(C H BrAl(C H were sealed, respectively. These ampoules wereput in a 300 cc. stainless steel shaking-type autoclave 150 cc. ofn-heptane was also added to it. The autoclave was closed, cooled to 80C. and evacuated. Then, 25 g. of purity propylene, (the remainingcomponents are mainly propane and butane) was introduced. The auto-Example 7 In two pieces of 10 cc. glass ampoules, 0.6 m. mole of finelydivided TiCl and 1.0 m. mole of the complex Sb(C H BrAl (C H Br,synthesized according to the process of the present invention, wereseparately sealed. The analytical values and physical properties of saidcomplex were as fOllW&-

Analytical values:

Sb l Al C H 131 Calcd (percent) 20. 40 9. 04 36. 23 7. 55 26. 78 Found(pereent) I 19. 96 9. 2O 36. 37 7. 66 216. 35

Physical properties D435, 1.312 11,13 1.5200.

These ampoules were placed in a 300 cc. stainless steel shaking typeautoclave, which was then closed after the addition 150 cc. of n-hexane.After the autoclave was cooled to 80 C. and evacuated, 25 g. of highpurity propylene was charged. Subsequently, the autoclave was heated to55 C. and the ampoules were broken, the polymerization was carried outfor 3 hours while shaking the autoclave. The resulting polymerizationproduct was treated by the same methods as in Example 1 to obtain 20.3g. of white powdery polymer. Its n-heptane extraction residue was 92.5%and its intrinsic viscosity was 9.23.

Example 8 The same polymerization of propylene as in Example 7 wasrepeated except that, in place of Sb 111 C H 01 Gale (1 (percent) 18. 007. 98 53. 26 10. 28 1 0. 48 Found (percent)--. 18. 64 8. 07 52. 25 10.21 10. 74

Physical properties D49 1.066 7111 1.4880.

This polymerization yielded 19.5 g. of white powdery polymer. I-tsn-heptane extraction residue was 91.3% and its intrinsic viscosity was8.56.

Example 9 The same polymerization of propylene as in Example 7 wasrepeated except that, instead of Sb (C H BrAl (C H Br the complexsynthesized according to the process described in the body of thepresent specification, was employed. The analytical values and physicalproperties of said complex were as f-ollows- Analytical values:

Sb Al O H 01 Calcd (percent)... 18. 00 7. 98 53. 26 10. 28 10. 48 Found(porcent) 18. 35 7. 68 52. 28 10. 45 11. 10

Physical properties Dr, 1034 an. 1.4872.

20.0 g. of a white powdery polymer was obtained and its n-heptaneextraction residue was 91.5%, while its intrinsic viscosity was 9.24.

Example 10 The same polymerization of propylene as in Example 7 waseffected except that, in place of the ComplexSb(C2H5)4C1A12(C2H5)3(i-C4H9)3, Synthesized according to the processdescribed in the body of the present specification, was employed. Theanalytical values and physical properties of said complex were asfollows Analytical values:

Sb A1 I O H 01 Oalcd (percent) 20.87 9. 21 53. 29 10. 67 6. 05 Found(percent)-.. 20. 9. 56 53. 70 10. 59 6.80

Physical properties D435, 1.027 no, 1.4922.

19.3 g. of white powdery polymer was obtained, and its n-heptaneextraction residue was 93.2%, While its intrinsic viscosity was 9.35.

Example 11 The same polymerization of propylene as in Example 7 wasconducted except that, instead of Sb (C H BrAl (C H Br the complex Sb(CH ClA1 (C I-l (C H synthesized according to the process described in thepresent specification was used. The analytical values and physicalproperties were as follows Analytical values:

I Sb I Al O H 01 Calcd (percent) 18. 17 8. 05 57. 36 11. 13 5. 29 Found(percent). 18. 48 8. 10 57. 29 11. 42 4. 75

Physical properties: D 0.989; 11, 1.4876.

19.0 g. of white powdery polymer was obtained, and its n-heptaneextraction residue was 96.6%, while its intrinsic viscosity was 8.72.

Example 12 0.5 mole of high purity butene 1 was polymerized 'accordingto the process and the polymerization conditions adopted in Example 7except that, in place of 0.3 mole of high purity styrene was polymerizedin accordance with the same method and the polymerization conditions asshown in Example 7, except that the complex employed in Example 1, i.e.,Sb.(C H ClAl (C H C1, was used in place of Sb(C H BrAl (C H Br, whilemaintaining the polymerization temperature at 70 C.

In a 20 cc. glass ampoule, 0.3 m. mole of finely powdered TiCl and 0.7m. mole of the complex employed in Example 3, were sealed together with7 cc. of cyclohexane under dried oxygen-free nitrogen atmosphere. Thisampoule was placed in a 300 cc. stainless steel shaking type autoclave,which was closed after the addition of 150 cc. of purified driedcyclohexane. After evacuating, the autoclave was heated to 90 C. intowhich a high purity propylene was introduced under pressure so as tomaintain the partial pressure at 10 kg./cm' and the ampoule was broken,whereby the polymerization was continued for 2 hours while shaking theautoclave. The resulting polymerization product was treated according toExample 1 to obtain 30 g. of white powdery polymer. The polymer obtainedshowed the n-heptane extraction residue of 87.3% and the intrinsicviscosity of 5.32.

Example 15 In a 20 cc. glass ampoule, 1.0 m. mole of finely powderedTiCl and 0.7 m. mole of the complex employed in Example 3, i.e.,Sb(C2H5)4C1Al2(C4H5) were sealed together with 7 cc. of n-heptane. Thisampoule was put in a 300 cc. stainless steel shaking type autoclave,which was closed after the addition of 150 cc. of purified and driedn-heptane. evacuating, the autoclave was heated to 55 C. into which ahigh purity propylene was introduced under pressure so as to maintainthe partial pressure at 1.0 kg./cm. and the ampoule was broken, wherebythe polymerization was continued for hours while shaking the autoclave.The

resulting polymerization product was treated according to the processshown in Example 1 to obtain 35 g. of white powdery polymer. Then-heptane extraction residue of this polymer was 94.2% while itsintrinsic viscosity was 5.46.

Example 16 Into a 30 1. stainless steel reactor provided with a stirrer,15 l. of xylene was introduced. Subsequently, 6.75 g. of finely powderedtitanium trichloride and 20 g. of the complex employed Example 3, i.e.,

were added to the reactor. Then, high purity propylene was introducedunder pressure into the reactor so as to maintain the partial pressureat 3.0 kg./cm. and the polymerization was carried out at 55 C. for 3hours while agitating. After the polymerization, methanol was chargedinto the reactor to decompose the residual catalyst. The resulting whitepowdery polymer was washed Int-o a 300 cc. stainless steel autoclave,150 cc. of nhexane was charged, and then 2.5 m. mole of finely dividedtitanium trichloride, obtained by reducing titanium tetrachloride withhydrogen, was introduced under dried oxygen free nitrogen atmosphere.Subsequently, the complex Sb(C H lAl(C H synthesized according to theprocess disclosed in the body of the presznt After cooling to 80 C. and

specification, was charged into the autoclave, which was then closed.The above-mentioned complex was colorless liquid having the followinganalytical value:

Sb Al 1 I O I H Calcd (percent) 24. 38 5. 54 27. 06 34. 50 8. 26 Found(percent) 25. 42 5. 64 26. 49 35. 10 7. 36

The resulting mixture was stirred for 5 minutes at room temperature andcooled to C. After evacuating the autoclave, 0.5 mole of high puritypropylene was charged therein. Subsequently, the autoclave was heated to60 C. and the polymerization was carried out for 5 hours while shakingthe autoclave. The polymerization pressure showed 6.3 kg./cm. at firstbut completely lowered in 3 hours. Basing upon the variation of thepolymerization pressure, quantity of the produced polymer per gram Intwo 10 cc. glass ampoules, 2.5 m. moles of finely powdered TiCl and 2.5m. moles of the complex synthesized according to the process disclosedin the body of the present specification were sealed, respectively,under dried oxygen free nitrogen atmosphere. The above- T mentionedcomplex was colorless liquid having the following analytical values:

Sb I A1 C1 1 O H Calcd (percent) .41 6 96 9.15 43. 38 9.10 Found(percent) 31. 47 6. 9. 35 42. 59 9. 12

Example 19 The same polymerization of propylene as in Example 17 wascarried out at 15 C. for 15 hours, employing the complex Sb (S H ClAl(CH Cl in place of This complex was colorless liquid having the followinganalytical values:

Sb Al Cl C II Calcd (percent).-- 30. 90 6 85 18.00 36. 58 7. 67 Found(percent) 31.16 6. 61 19.09 35. 59 7. 57

In this case also white powdery polymer was obtained quantitatively. Itsn-heptane extraction residue was 96.7% and its intrinsic viscosity intetraline solution at C. was 10.0.

15 Example 20 The same polymerization of propylene as in Example 17 wasconducted except that the complex MQ Q)3( 2 3 T)3 was employed in placeof Sb(C H IAl(C H The said complex was colorless liquid having thefollowing analytical values:

In this case also white powdery polymer was obtained quantitatively, andits n-heptane extraction residue was 85%, while its intrinsic viscosityin tetraline solution at 135 C. was 7.38.

Example 21 In two cc. glass ampoules, 2.5 m. molds of finely powderedttanium trichloride (corresponding to (TiCl AlCl obtained by reducingtitanium tetrachloride with metallic Al and 5.0 m. moles of the complexsynthesized according to the process described in the body of thepresent specification, were sealed separately. This complex was whitecrystals (M.P. 3436 C.) having the following analytical values:

Sb Al G1 I C l H Calcd (percent)- 30. 41 6. 74 26. 57 29.97 6. 29 Found(percent) 29. 69 6. 59 261 90 28. 49 5. 96

The aforesaid ampoules were placed in a 300 cc. stainless steelautoclave, which was then evacuated. Into the auoclave, 150 cc. ofpurified n-hexane was introduced and then 0.5 mole of high puritypropylene was charged. Subsequently, the autoclave was heated to 60 C.and shaken to break the ampoules, whereby the polymerization was carriedout for hours. The resulting polymerization product was treated by thesame methods as in Example 1 to obtain 17.5 g. of white powdery polymer.The n-hepta-ne extraction residue of the polymer showed a value of ashigh as 94.3% and the intrinsic viscosity thereof in tetraline solutionat 135 C. was 13.8.

Example 22 In two pieces of 10 cc. glass ampoules, 5.0 m. moles offinely powdered TiCl obtained by reducing TiCL; with aluminum metal and5 .0 m. moles of employed in Example 1, were sealed separately underoxygen-free nitrogen atmosphere. These tampoules were put in a 300 cc.stainless steel autoclave, to which was then introduced .150 cc. ofpurified and dried n-hexane. After evacuating the autoclave, 30 g. ofhigh purity 3- methyl butene-l was charged therein. The autoclave wasthen heated to 70 C. and the am-poules were broken to :start thepolymerization. After 15 hours polymerization while shaking theautoclave, the polymerization product was treated by the same methods asdescribed in Example 1 to obtain 30 g. of white powdery polymer. Then-heptane extraction residue of said polymer was 94%.

Example 23 Exactly the same polymerization as in Example 22. was carriedout except that 4-methyl-pentene-1 was employed instead of3-methyl-butene-1 to obtain g. of white powdery polymer. The n-heptaneextraction residue of said polymer was 90%.

Referential example Exactly the same polymerization of propylene as inExample 3 was repeated except that 5.0 m. moles of Al(C H was used inplace of 2.5 [11. moles of The n-heptane extraction residue of theresulting white powdery polymer was 65.5% while the intrinsic viscositythereof was 3.05.

What we claim is:

1. A method tor producing a poly-wolefin which comprises polymerizing anOL-Qlfin selected from the group consisting of propylene, ibutene-l,pentene-l, 3-methylbutene-l, 4-methyl-pentene-1 and styrene, in thepresence of a catalyst prepared by reacting (A) titanium trichloridewith (B) one organo-metallic complex selected from the group consistingof:

wherein X represents one member selected from the group consisting of Cland Br; R represents an ethyl group; and R represents an alkyl grouphaving 2 to 6 carbon atoms and the number of the alkyl group having atleast 4 carbon atoms is limited to at most 3, (2) SbR XAl R' X,

wherein X and X represent respectively members selected from the groupconsisting of Cl and Br; R represents an ethyl group; R represents analkyl group having 2 to 6 carbon atoms and the number of the alkyl grouphaving at least 5 carbon atoms is limited to at most 2; and R"represents an alkyl group having 2 to 6 carbon atoms,

wherein X and X represent respectively members selected from the groupconsisting of Cl, Br and I; R and R represent respectively alkyl groupshaving 1 to 6 carbon atoms; and n is an integer between 1 and 3, themole ratio of said organo metallic complex to titanium trichloride being(Ll-10:1.

2. A method according to claim 1, wherein the organo-metallic complex ofS'bR XAl R' is selected from the group consisting of:

3. A method according to claim 1, wherein the organo-metallic complex ofSbR R"XAl R X is selected from the group consisting of:

4. A method according to claim 1, wherein the organo-metallic complex ofSblR.,,XAlR X';, is selected from the group consisting of:

5. Amethod according to claim 1, wherein the polymerization is effectedin the polymerization medium selected from the group consisting ofn-heptane, benzene, xylene and cyclohexane.

6. A method according to claim 1, wherein the polymerization is carriedout at a temperature between 40 C. and C. while maintaining the partialpressure of the olefin at 1 to 10 atm.

7. A method according to claim 1, wherein highly crystallinepolypropylene is produced by polymerizing proplyene in the presence of acatalyst comprising 1 mole of titanium trichlor-ide and 2 moles of 8. Amethod according to claim 1, wherein highly crystallinepolypropylene isproduced by polymerizing propylene in the presence of a catalystcomprising 1 mole of titanium tr-ichloride and 2 moles of Sb C H ClAl (CH C1 9. A method according to claim 1, wherein highly crystallinepolypropylene is produced by polymerizing propylene in the presence of acatalyst comprising 1 mole of titanium trichlor-ide and 2 moles of 10. Amethod according to claim 1, wherein highly crystalline polybutene-l isproduced by polymerizing butene-l in the presence of a catalystcomprising 1 mole of titanium trichloride and 2 moles of 11. A methodaccording to claim 1, wherein highly crystalline polystyrene is producedby polymerizing styrene in the presence of a catalyst comprising 1 moleof titanium trichloride and 2 moles of 18 metallic complex selected fromthe group consisting of:

(1) SbR XAl R' wherein X represents one member selected from the groupconsisting of Cl and Br; R represents an ethyl group; and R representsan alkyl group having 2 to 6 carbon atoms and the number of the alkylgroup having at least 4 carbon atoms is limited to at most 3, (2) SbR"XAl R' X',

wherein X and X represent respectively members selected from the groupconsisting of Cl and Br; R represents an ethyl group; R represents analkyl group having 2 to 6 carbon atoms and the number of the alkyl grouphaving at least 5 carbon atoms is limited to at most 2; and R"represents an alkyl group having 2 to 6 carbon atoms, and (3) SbR XA1R'X' wherein X and X represent respectively members selected from thegroup consisting of Cl, Br and I; R and R represent respectively alkylgroups having 1 to 6 carbon atoms; and n is an integer of 1, 2 and 3,the mole ratio of said organo-rnetallic complex to titanium trichloridebeing 0.1-10:1.

References Cited by the Examiner UNITED STATES PATENTS 3,058,963 10/1962 Vandenberg 260-94 3,081,287 3/ 1963 Cover et al 252429 3,118,8651/1964 Bruce et al 252429 FOREIGN PATENTS 233,098 3/ 1961 Australia.

JOSEPH L. SCHOFER, Primary Examiner.

JAMES A. SEIDLECK, HARRY WONG, Examiners.

1. A METHOD FOR PRODUCING A POLY-A-OLEFIN WHICH COMPRISES POLYMERIZINGAN A-OLEFINN SELECTED FROM THE GROUP CONSISTING OF PROPYLENE, BUTENE-1,PENTENO-1, 3-METHYLBUTENE-1, 4-METHYL-PENTENE-1 AND STYRENE, IN THEPRESENCE OF A CATALYST PREPARED BY REACTING (A) TITANIUM TRICHLORIDEWITH (B) ONE ORGANO-METALLIC COMPLEX SELECTED FROM THE GROUP CONSISTINGOF: (1) SBR4XAI2R''6, WHEREIN X REPRESENTS ONE MEMBER SELECTED FROM THEGROUP CONSISTING OF CI AND BR; R REPRESENTS AN ETHYL GROUP; AND R''REPRESENTS AN ALKYL GROUP HAING 2 TO 6 CARBON AOMS AND THE NUMBER OF THEALKYL GROUP HAVING AT LEAST 4 CARBON ATOMS IS LIMITED TO AT MOST 3, (2)SBR3''''XAI2R''X'', WHEREIN X AND X'' REPRESENT RESPECTIVELY MEMBERSSELECTED FROM THE GROUP CONSISTING OF CI AND BR; R REPRESENTS AN ETHYLGROUP; R'' REPRESENTS AN ALKYL GROUP HAVING 2 TO 6 CARBON ATOMS AND THENUMBER OF THE ALKYL GROUP HAVING AT LEAST 5 CARBON ATOMS IS LIMITED TOAT MOST 2; AND R" REPRESENTED AN ALKYL GROUP HAVING 2 TO 6 CARBON ATOMS,(3) SBR4XAIR''NX''3-N, WHEREIN X AND X'' REPRESENT RESPECTIVELY MEMBERSSELECTED FROM THE GROUP CONSISTING OF CI, BR AND I; R AND R'' REPRESENTRESPECTIVELY ALKYL GROUPS HAVING 1 TO 6 CARBON ATOMS; AND N IS ANINTEGER BETWEEN 1 AND 3, THE MOLE RATIO OF SAID ORGANO METALLIC COMPLEXTO TITANIUM TRICHLORIDE BEING 0.1-10:1.